EP0231894A1 - Verfahren zur Herstellung eines Kohlenstoffilmes - Google Patents

Verfahren zur Herstellung eines Kohlenstoffilmes Download PDF

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Publication number
EP0231894A1
EP0231894A1 EP87101271A EP87101271A EP0231894A1 EP 0231894 A1 EP0231894 A1 EP 0231894A1 EP 87101271 A EP87101271 A EP 87101271A EP 87101271 A EP87101271 A EP 87101271A EP 0231894 A1 EP0231894 A1 EP 0231894A1
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Prior art keywords
carbon films
carbon
ppm
torr
mixed gas
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EP87101271A
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English (en)
French (fr)
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EP0231894B1 (de
Inventor
Misuzu Watanabe
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Meidensha Corp
Meidensha Electric Manufacturing Co Ltd
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Meidensha Corp
Meidensha Electric Manufacturing Co Ltd
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Priority claimed from JP61019570A external-priority patent/JPS62180057A/ja
Priority claimed from JP61019569A external-priority patent/JPH0742570B2/ja
Priority claimed from JP61019568A external-priority patent/JPS62180055A/ja
Priority claimed from JP61019567A external-priority patent/JPS62180054A/ja
Priority claimed from JP1956686A external-priority patent/JPH079059B2/ja
Application filed by Meidensha Corp, Meidensha Electric Manufacturing Co Ltd filed Critical Meidensha Corp
Publication of EP0231894A1 publication Critical patent/EP0231894A1/de
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon

Definitions

  • This invention relates to a method of producing a carbon film on a substrate and, more particularly, to a carbon film producing method utilizing a reactive sputtering process for releasing carbon particles from a graphite target electrode to deposite a carbon film on a substrate.
  • the plasma CVD method utilizes a plasma to decompose hydrocarbon gas (carbon source) into carbon atomic particles.
  • hydrocarbon gas carbon source
  • the plasma CV D method requires the substrate temperature to be maintained above 20 0 0 C. Therefore, this method is not applicable to substrates which cannot tolerate such high temperatures.
  • a method of producing a carbon film on a substrate comprises the steps of placing the substrate in a vacuum chamber having a graphite target electrode and an opposite electrode placed therein, evacuating the vacuum chamber to a predetermined pressure, introducing a gaseous mixture into the vacuum chamber to produce a gaseous atmosphere therein at a pressure ranging from 0. 7 Pa to 665 Pa, the gaseous mixture includes a kind of gas mixed at a predetermined ratio to hydrogen gas, and releasing atomic particles from the graphite target electrode through a reactive sputtering process performed in the gaseous atmosphere, thereby depositing a carbon film on the substrate.
  • the sputtering device includes a vacuum vessel, designated generally by the numeral 10, which includes a cylindrical metal body 12 closed at its opposite ends with upper and lower metal covers 14 and 16 to def ine a vacuum chamber therein.
  • An O-ring 20 is provided to prevent leakage between the upper cover 14 and the cylindrical body upper end.
  • an 0-ring 22 is provided to prevent leakage between the lower cover 16 and the cylindrical body lower end.
  • the lower cover 16 is formed centrally with an opening through which an exhaust pipe 24 opens into the vacuum chamber.
  • the exhaust pipe 24 is connected to a vacuum pump (not shown) which is operable to evacuate the vacuum chamber and keep it at a high vacuum.
  • a gas mixture is introduced through a gas inlet pipe 26 to provide an atmosphere of the gas mixture in the vacuum chamber.
  • the gas inlet pipe 26 extends through the cylindrical body wall at a position near the upper cover 14.
  • a coolant pipe 30 extends through the cylindrical body 12 into the vacuum chamber and terminates in an upward facing flange 32 on which an electrode box 40 is placed.
  • a seal is provided to prevent leakage between the coolant pipe 30 and the cylindrical body wall.
  • the electrode box 40 has a magnetron 42 including a permanent magnet placed therein and a graphite target or cathode electrode 44 supported thereon. The magnetron 40 is operable to create a magnetic field.
  • the coolant pipe 30 has a coolant supply pipe 34 extending inside the coolant pipe 30 from a coolant inlet port 35 into the electrode box 4 0 , and a coolant discharge pipe 36 defined outside the coolant supply pipe 34.
  • the coolant discharge pipe 36 extends from the electrode box 40 to a coolant discharge port 37.
  • the coolant inlet port 35 is connected to a pump (not shown) which is operable to introduce a coolant, such for example as water, through the coolant supply pipe 3 4 for cooling the magnetron 42 and graphite target electrode 44.
  • a coolant such for example as water
  • the coolant is discharged from the electrode box 40 through the coolant discharge pipe 36 to the coolant discharge port 37.
  • An anode or opposite electrode 46 which is secured and grounded through a conductive rod 4 8 to the upper cover 14, is positioned in a parallel-spaced relation to the graphite target electrode 44.
  • the target electrode 44 is electrically connected to an RF power source (not shown) through the electrode box 40 and the coolant pipe 30.
  • a support plate 50 insulated electrically from the ground potential, is secured on the inner surface of the upper cover 14.
  • the support plate 50 is shown as having two glass substrates 62 fixed thereon by the aid of retainers 52.
  • Another support plate 54 insulated electrically from the ground potential, is secured on the inner surface of the cylindrical body 12.
  • the support plate 54 is shown as having two glass substrate 64 secured thereon by the aid of retainers 56.
  • Another glass substrate 66 is fixed on the opposite electrode 46 by the aid of retainers 58.
  • the reference numeral 70 designates a thermocouple for measuring the temperature of the glass substrate 62. Similar thermocouples may be provided for measuring the temperatures of the other glass substrates.
  • a gas mixture is introduced through the gas inlet pipe 26 to produce a gaseous atmosphere at a predetermined pressure in the vacuum chamber.
  • a sputtering operation is started by applying a high-frequency (radio frequency) power between the target and opposite electrodes 44 and 46.
  • a plasma is generated in the domain A indicated by an inner broken circle between the electrodes 44 and 46 to release carbon atomic particles from the graphite target electrode 44.
  • the released atomic particles pass through the domain B indicated by an outer broken circle to the domain C where they are deposit themselves relatively softly in the form of a carbon film having diamond or amorphous formation on the glass substrates 62 and 64 placed in the domain C outside the domain B. It is to be noted that, since most of the atomic particles that pass into the domain C, are charged particles and therefore subjective to the influence of electric fields, the substrates 6 2 and 64 should be located at positions having a uniform potential, such as near a ground potential for example.
  • the vacuum chamber was evacuated to a pressure of 1 . 33 x 10 -5 Pa (10 -7 Torr) and then a diborane (B 2 H 6 ) and hydrogen (H 2 ) gas mixture having a mixing ratio (B 2 H 6 /H 2 ) of 10 ppm was introduced through the gas inlet pipe 26 into the vacuum chamber until the vacuum chamber pressure increased to 67 Pa (0.5 Torr).
  • a sputtering operation was started by supplying a power having a frequency of 13.56 MHz to the target electrode 44. The sputtering operation was continued for 9 hours while controlling the high-frequency current in such a manner as to produce an electric power of 6.8 W/cm 2 at the graphite target electrode 44.
  • light-yellow or colorless, transparent carbon films were produced on the respective glass substrates 62. 64 and 66.
  • the temperatures of the glass substrates 62, 64 and 66 were 80°C or less, 80°C or less, 180°C, respectively. This indicates that the sputtering can be made under low temperature if the glass substrates are placed on the domain C.
  • the forces of adhesion of the carbon films to the respective glass substrates were tested by applying and then exfoliating an adhesive tape on each of the carbon films. None of the carbon films became separated from the respective glass substrates. In the exfoliation tests, the adhesion of the carbon films produced on the glass substrate 66 proved to be superior to that of the carbon films produced on the other glass substrates 62 and 64.
  • the carbon films produced on the glass substrate 62 exhibited a specific electrical resistance greater than 1 x 10 12 ⁇ .cm
  • the carbon films produced on the glass substrate 64 exhibited a specific resistance greater than 1 x 10 12 ⁇ .cm
  • the carbon films produced on the glass substrate 66 exhibited a specific resistance of 1 x 10 11 ⁇ .cm.
  • Carbon films were produced by the sputtering method under the same conditions except that only hydrogen gas was introduced to produce an atmosphere of hydrogen in the vacuum chamber.
  • the carbon films produced on the glass substrate 62 exhibited a specific resistance of 1 x 10 11 ⁇ .cm or more
  • the carbon films produced on the glass substrate 64 exhibited a specific resistance of 1 x 10 11 ⁇ .cm or more
  • the carbon films produced on the glass substrate 66 exhibited a specific resistance of 6 x 10 10 ⁇ .cm. It can be seen that the carbon films produced in an atmosphere of diborane and hydrogen have a higher specific resistance than the carbon films produced in an atmosphere of hydrogen only.
  • Curve A illustrates carbon films produced at a mixed gas pressure of 40.0 Pa (0.3 Torr)
  • curve B illustrates carbon films produced at a mixed gas pressure of 66.7 Pa (0.5 Torr)
  • curve C illustrates carbon films produced at a mixed gas pressure of 100 Pa (0.75 Torr)
  • curve D illustrates carbon films produced at a mixed gas pressure of 267 Pa (2.0 Torr).
  • the test results have proved to be substantially similar to the results of tests conducted on carbon films produced under the same conditions ex-cept that only hydrogen gas was introduced to provide a gaseous atmosphere in the vacuum chamber.
  • the white points indicate optical band-gap values plotted with respect to given values of mixed gas pressure and the black points indicate spin density values plotted with respect to given values of mixed gas pressure.
  • the carbon films produced according to the method of the invention have a good optical band-gap ranging from 2.05 to 3.15 eV and a small spin density ranging from 2 x 10 16 to 3 x 10 17 /cm 3. It is, therefore, possible to provide a semiconductor having a desired characteristic by doping small quantities of impurities to the carbon film.
  • Fig. 5 illustrates the results of a number of further tests which were conducted to show the effect of gas mixing ratio (B2H6/H2) on carbon film specific resistance.
  • the gas mixing ratio was changed in a range from 1 to 20 ppm while the mixed gas pressure was held at 66.7 Pa.
  • the gas mixing ratio ranging from 1 to 20 ppm has proven satisfactory. If the gas mixing ratio is smaller than this range, the carbon film specific resistance becomes too small. If it is greater than he range, the semiconductor effect will decrease the carbon film specific resistance to a level that is less than the specific resistance of carbon films produced by the sputtering method in an atmosphere of hydrogen only.
  • the diborane and hydrogen gas mixture be held at a pressure ranging from 0.7 Pa to 665 Pa (5 Torr). If the mixed gas pressure is smaller than this range, the carbon films will exhibit a low specific resistance and an undesirable spin density. If it is greater than the range, the infrared spectrum will have a greater absorption coefficient at a 2960 cm -1 wave number, as shown in Fig. 2, causing a film quantity change and a spin density increase.
  • the vacuum chamber was evaucated to a pressure of 1 . 33 x 10 - 5 Pa ( 10 -7 Torr) and then a oxygen (0 2 ) and hydrogen (H 2 ) gas mixture having a mixing ratio (0 2 /H 2 ) of 25 ppm was introduced through the gas inlet pipe 26 into the vacuum chamber until the vacuum chamber pressure increased to 67 Pa (0.5 Torr).
  • a sputtering operation as started by supplying a high-frequency power having a frequency of 13.56 MHz to the target electrode 44. The sputtering operation was continued for 9 hours while controlling the high-frequency current in a manner to produce an electric power of 6. 8 W/cm for the graphite target electrode 44.
  • the white points indicate optical band-gap values plotted with respect to given .values of mixed gas pressure and the black points indicate spin density values plotted with respect to given values of mixed gas pressure.
  • the carbon film produced according to the method of the invention has a good optical band-gap ranging from 2.05 to 3.15 eV and a small spin density ranging from 2 x 10 16 to 3 x 10 17 /cm 3 . It is, therefore, possible to provide a semiconductor having a desired characteristic by doping small quantities of impurities to the carbon film.
  • Fig. 9 illustrates the results of a number of further tests which were conducted to show the effect of gas mixing ratio (0 2 /H Z ) on carbon film specific resistance.
  • the gas mixing ratio was varied through a range from 1 to 100 ppm has proven satisfactory. If the gas mixing ratio is smaller than this range, the carbon film specific resistance is too small. If it is greater than the range, the carbon film specific resistance will decrease to a level less than the specific resistance of carbon films produced by the sputtering method in a hydrogen only atmosphere.
  • the oxygen and hydrogen gases mixture be held at a pressure ranging from 0.7 Pa to 665 Pa (5 Torr). If the mixed gas pressure is smaller than this range, the carbon films will exhibit a low specific resistance and an undesirable spin density. If it is greater than the range, the infrared spectrum will have a greater absorption coefficient at a 2960 cm -1 wave number, as shown in Fig. 6, causing a film quantity change and a spin density increase.
  • the vacuum chamber was evacuated to a pressure of 1.33 x 10 - 5 Pa (10 -7 Torr) and then fluorine (F 2 ) and hydrogen (H 2 ) gases mixed at a mixing ratio (F 2 /H 2 ) of 10 ppm was introduced through the gas inlet pipe 26 into the vacuum chamber until the vacuum chamber pressure increases to 67 Pa (0.5 Torr).
  • a sputtering operation as started by supplying a high-frequency power having a frequency of 13.56 MHz to the target electrode 44.
  • the sputtering operation as continued for 9 hours while controlling the high-frequency current in a manner to produce an electric power of 6.8 W/cm at the graphite target electrode 44.
  • light-yellow or colorless, transparent carbon films were produced on the respective glass substrates 62, 64 and 66.
  • the temperatures of the glass substrates 62, 64 and 66 were 8 0°C or less, 80°C or less, 180 0 C, respectively. This indicates that the sputtering can be made under low temperature if the glass substrates are placed on the domain C.
  • the forces of adhesion of the carbon films to the respective glass substrates were tested by applying and exfoliating an adhesive tape on each carbon films. None of the carbon films were separated from the respective glass substrates. In the exfoliation tests. the carbon films produced on the glass substrate 66 has proven superior to the carbon films produced on the other glass substrates 62 and 64.
  • the carbon films produced on the glass substrate 62 exhibited a specific resistance greater than 1 x 10 12 ⁇ .cm
  • the carbon films produced on the glass substrate 64 exhibited a specific resistance greater than 1 x 1 0 12 ⁇ .cm
  • the carbon films produced on the glass substrate 66 exhibited a specific resistance of 1 x 10 11 ⁇ .cm.
  • Carbon films were produced by the sputtering method under the same conditions except that only hydrogen gas was introduced to produce an atmosphere of hydrogen in the vacuum chamber.
  • the carbon films produced on the glass substrate 62 exhibited a specific resistance of 1 x 10 11 ⁇ .cm or more
  • the carbon films produced on the glass substrate 64 exhibited a specific resistance of 1 x 10 11 ⁇ .cm or more
  • the carbon films produced on the glass substrate 66 exhibited a specific resistance of 6 x 10 10 ⁇ .cm. It can be seen that the carbon films produced in an atmosphere of fluorine and hydrogen have a higher specific resistance than the carbon films produced in an atmosphere of hydrogen only.
  • Curve A illustrates carbon films produced at a mixed gas pressure of 40.0 Pa (0.3 Torr)
  • curve B illustrates carbon films produced at a mixed gas pressure of 66.7 Pa (0.5 Torr)
  • curve C illustrates carbon films produced at a mixed gas pressure of 100 Pa (0.75 Torr).
  • curve D illustrates carbon films produced at a mixed gas pressure of 267 Pa (2.0 Torr).
  • the white points indicate optical band-gap values plotted with respect to given values of mixed gas pressure and the black points indicate spin density values plotted with respect to given values of mixed gas pressure.
  • the carbon film produced according to the method of the invention has a good optical band-gap ranging from 2.05 to 3.15 eV and a small spin density ranging from 2 x 10 16 to 3 x 10 17 /cm 3 . It is, therefore, possible to provide a semiconductor having a desired characteristic by doping small quantities of impurities to the carbon film.
  • Fig. 13 illustrates the results of a number of further tests which were conducted to show the effect of gas mixing ratio (F 2 /H 2 ) on carbon film specific resistance.
  • the gas mixing ratio was changed in a range from 1 to 100 ppm while the mixed gas pressure was held at 66.7 Pa.
  • the gas mixing ratio ranging from 1 to 100 ppm has proven satisfactory. If the gas mixing ratio is smaller than this range, the carbon film specific resistance is too small. If it is greater than the range, there will be a greater tendency of the fluorine gas to corrode the vacuum vessel 10 made of SUS304 or SUS316.
  • the fluorine and hydrogen gas mixture be held at a pressure ranging from 0.7 Pa to 665 P a (5 Torr). If the mixed gas pressure is smaller than this range, the carbon films will exhibit a low specific resistance and an undesirable spin density. If it is greater than the range, the infrared spectrum will have a greater absorption coefficient at a 2960 cm -1 wave number. as shown in Fig. 10. causing a film quantity change and a spin density increase.
  • the vacuum chamber was evacuated to a pressure of 1 . 33 x 10 -5 Pa (10 -7 Torr) and then nitrogen (N 2 ) and hydrogen (H 2 ) gases mixed at a mixing ratio (N Z /H 2 ) of 25 ppm was introduced through the gas inlet pipe 26 into the vacuum chamber until the vacuum chamber pressure increases to 67 Pa (0.5 Torr).
  • a sputtering operation was started by supplying a high-frequency power having a frequency of 13.56 MHz to the target electrode 4 4.
  • the sputtering operation as continued for 9 hours while controlling the high-frequency current in a manner to produce an electric power of 6.8 W/cm 2 for the graphite target electrode 44.
  • light-yellow or colorless, transparent carbon films were produced on the respective glass substrates 62, 64 and 66.
  • the temperatures of the glass substrates 62, 64 and 66 were 80 0 C or less, 80°C or less, 180°C, respectively. This indicates that the sputtering can be made under low temperature if the glass substrates are placed on the domain C.
  • the forces of adhesion of the carbon films to .the respective glass substrates were tested by exfoliating an adhesive tape sticked on each carbon films. None of the carbon films were separated from the respective glass substrates. In the exfoliation tests, the carbon films produced on the glass substrate 66 has proven superior to the carbon films produced on the other glass substrates 62 and 64.
  • the carbon films produced on the glass substrate 62 exhibited a specific resistance greater than 1 x 10 12 ⁇ .cm
  • the carbon films produced on the glass substrate 64 exhibited a specific resistnce greater than 1 x 10 12 ⁇ .cm
  • the carbon films produced on the glass substrate 66 exhibited a specific resistance of 1 x 10 11 0 .cm.
  • Carbon films were produced by the sputtering method under the same conditions except that only hydrogen gas was introduced to produce an atmosphere of hydrogen in the vacuum chamber.
  • the carbon films produced on the glass substrate 62 exhibited a specific resistance of 1 x 10 11 ⁇ .cm or more
  • the carbon films produced on the glass substrate 64 exhibited a specific resistance of 1 x 10 11 ⁇ .cm or more
  • the carbon films produced on the glass substrate 66 exhibited a specific resistance of 6 x 10 10 ⁇ .cm. It can be seen that the carbon films produced in an atmosphere of nitrogen and hydrogen have a higher specific resistance than the carbon films produced in an atmosphere of hydrogen only.
  • Curve A illustrates carbon films produced at a mixed gas pressure of 40.0 Pa (0.3 Torr)
  • curve B illustrates carbon films produced at a mixed gas pressure of 66.7 Pa (0.5 Torr)
  • curve C illustrates carbon films produced at a mixed gas pressure of 100 Pa (0.75 Torr)
  • curve D illustrates carbon films produced at a mixed gas pressure of 267 Pa (2.0 Torr).
  • the carbon films produced by the method of the invention have high resistances. This corresponds to the fact that the carbon films are composed almost of SP couplings and they have less SP 2 couplings which cause insulation resistance reduction.
  • the white points indicate optical band-gap values plotted with respect to given values of mixed gas pressure and the black points indicate spin density values plotted with respect to given values of mixed gas pressure.
  • the carbon film produced according to the method of the invention has a good optical band-gap ranging from 2.05 to 3.15 eV and a small spin density ranging from 2 x 10 16 to 3 x 10 17 /cm 3 . It is, therefore, possible to provide a semiconductor having a desired characteristic by doping small quantities of impurities to the carbon film.
  • Fig. 17 illustrates the results of a number of further tests which were conducted to show the effect of gas mixing ratio (N 2 /H 2 ) on carbon film specific resistance.
  • the gas mixing ratio was changed in a range from 1 to 100 ppm while the mixed gas pressure was held at 66.7 Pa. The gas mixing ratio ranging from 1 to 100 ppm has proven satisfactory. If the gas mixing ratio is smaller than this range, the carbon film specific resistance is too small. If it is greater than the range, the carbon film specific resistance will be decreased to a level less than the specific resistance of carbon films produced by the sputtering method in an atmosphere of hydrogen only.
  • the mixed gas pressure be in the range from 0.7 Pa to 665 Pa (5 Torr). If the mixed gas pressure is smaller than this range, the carbon films will exhibit a low specific resistance and an undesirable spin density. If it is greater than the range. the infrared spectrum will have a greater absorption coefficient at a 2960 cm -1 wave number, as shown in Fig. 14, causing a film quantity change and a spin density increase.
  • the vacuum chamber was evacuated to a pressure of 1 . 33 x 10 -5 Pa (10 -7 Torr) and then tetrofluoromethane (CF 4 ) and hydrogen (H z ) gases mixed at a mixing ratio (CF 4 /H 2 ) of 5 ppm was introduced through the gas inlet pipe 26 into the vacuum chamber until the vacuum chamber pressure increases to 67 Pa (0.5 Torr).
  • a sputtering operation was started by supplying a high-frequency power having a frequency of 13. 5 6 M Hz to the target electrode 44.
  • the sputtering operation was continued for 9 hours while controlling the high-frequency current in a manner to produce an electric power of 6.8 W/cm 2 for the graphite target electrode 44.
  • light-yellow or colorless, transparent carbon films were produced on the respective glass substrates 62, 64 and 66.
  • the temperatures of the glass substrates 62, 64 and 66 were 80 0 C or less, 80°C or less, 180°C, respectively. This indicates that the sputtering can be made under low temperature if the glass substrates are placed on the domain C.
  • the forces of adhesion of the carbon films to the respective glass substrates were tested by exfoliating an adhesive tape sticked on each carbon films. None of the carbon films were separated from the respective glass substrates. In the exfoliation tests, the carbon films produced on the glass substrate 66 has proven superior to the carbon films produced on the other glass substrates 62 and 64.
  • the carbon films produced on the glass substrate 62 exhibited a specific resistance greater than 1 x 10 12 ⁇ .cm
  • the carbon films produced on the glass substrate 64 exhibited a specific resistance greater than 1 x 1012 ⁇ .cm
  • the carbon films produced on the glass substrate 66 exhibited a specific resistance of 1 x 10 11 ⁇ .cm.
  • Carbon films were produced by the sputtering method under the same conditions except that only hydrogen gas was introduced to produce an atmosphere of hydrogen in the vacuum chamber.
  • the carbon films produced on the glass substrate 62 exhibited a specific resistance of 1 x 10 11 ⁇ .cm or more
  • the carbon films produced on the glass substrate 64 exhibited a specific resistance of 1 x 10 11 ⁇ .cm or more
  • the carbon films produced on the glass substrate 66 exhibited a specific resistance of 6 x 10 10 ⁇ .cm. It can be seen that the carbon films produced in an atmosphere of tetrofluoromethane and hydrogen have a higher specific resistance than the carbon films produced .in an atmosphere of hydrogen only.
  • Curve A illustrates carbon films produced at a mixed gas pressure of 40.0 Pa (0.3 Torr).
  • curve B illustrates carbon films produced at a mixed gas pressure of 66.7 Pa (0.5 Torr).
  • curve C illustrates carbon films produced at a mixed gas pressure of 100 Pa (0.7 5 Torr), and curve D illustrates carbon films produced at a mixed gas pressure of 267 Pa (2.0 Torr).
  • P(CF4+H2), CF 4 /H 2 5 ppm
  • the white points indicate optical band-gap values plotted with respect to given values of mixed gas pressure and the black points indicate spin density values plotted with respect to given values of mixed gas pressure.
  • the carbon film produced according to the method of the invention has a good optical band-gap ranging from 2.05 to 3.15 eV and a small spin density ranging from 2 x 10 16 to 3 x 10 /cm . It is, therefore, possible to provide a semiconductor having a desired characteristic by doping small quantities of impurities to the carbon film.
  • Fig. 21 illustrates the results of a number of further tests which were conducted to show the effect of gas mixing ratio (CF 4 /H 2 ) on carbon film specific resistance.
  • the gas mixing ratio was changed in a range from 1 to 100 ppm while the mixed gas pressure was held at 66.7 Pa.
  • the gas mixing ratio ranging from 1 to 100 ppm has proven satisfactory. If the gas mixing ratio is smaller than this range, the carbon film specific resistance is too small. If it is greater than the range, there will be a greater tendency of the tetrofluoromethane gas to corrode the vacuum vessel.
  • the mixed gas pressure be in the range from 0.7 Pa to 665 Pa (5 Torr). If the mixed gas pressure is smaller than this range, the carbon films will exhibit a low specific resistance and an undesirable spin density. If it is greater than the range. the infrared spectrum will have a greater absorption coefficient at a 2960 cm -1 wave number, as shown in Fig. 18, causing a film quantity change and a spin density increase.
  • the tetrofluoromethane (CF 4 ) gas may be replaced by C 2 F 6 , C 3 F 8 , C 5 F 12 , CHF 3 . or other carbon fluoride gases to achieve the same result.
  • the inventive method can produce carbon films having desired characteristics through simple control.
  • the carbon films As a result, light-yellow or colorless, transparent carbon films were produced on the respective glass substrates 62, 64 an 66.
  • the temperatures of the glass substrates 62, 64 and 66 were 80°C or less 80°C or less, 180 0 C, respectively. This indicated that the sputtering operation can be performed at a relatively low temperature if the glass substrates are placed in domain C.
  • the forces of adhesion of the carbon films to the respective glass substrates were tested by applying and exfoliating an adhesive tape on each carbon films. None of the carbon films became separated from the respective glass substrates. In the exfoliation tests, the carbon films produced on the glass substrate 66 proved to be superior to the carbon films produced on the other glass substrates 62 and 64.
  • the carbon films produced on the glass substrate 62 exhibited a specific resistance greater than i x 10 12 ⁇ .cm
  • the carbon films produced on the glass substrate 64 exhibited a specific resistance greater than 1 x 1012 ⁇ .cm
  • the carbon films produced on the glass substrate 66 exhibited a specific electrical resistance of 1 x 10 11 ⁇ .cm.
  • Carbon films were produced by the sputtering method under the same conditions except that only hydrogen gas was introduced to produce an atmosphere of hydrogen in the vacuum chamber.
  • the carbon films produced on the glass substrate 62 exhibited a specific resistance of 1 x 1011 ⁇ .cm or more, the carbon films produced on the glass substrate 64 exhibited a specific resistance of 1 x 10 11 ⁇ .cm or more, and the carbon films produced on the glass substrate 66 exhibited a specific resistance of 6 x 10 10 ⁇ .cm. It can be seen that the carbon films produced in an atmosphere of oxygen and hydrogen have a higher specific resistance than the carbon films produced in an atmosphere of hydrogen only.
  • Curve A illustrates carbon films produced at a mixed gas pressure of 40.0 Pa (0.3 Torr)
  • curve B illustrates carbon films produced at a mixed gas pressure of 66. 7 Pa (0.5 Torr)
  • curve C illustrates carbon films produced at a mixed gas pressure of 100 Pa (0.75 Torr)
  • curve D illustrates carbon films produced at a mixed gas pressure of 267 Pa (2.0 Torr).
  • Fig. 7 illustrates the results of a number of tests which were conducted at different mixed gas pressures including 1.33 Pa (0.01 Torr). 6.67 Pa (0.05 Torr), 13.3 Pa (0.1 Torr), 40.0 Pa (0.3 Torr), 1 00 Pa (0.75 Torr), 133 Pa (1.0 Torr), 200 Pa (1.5 Torr) and 267 include less S p2 couplings and have a high specific resistance. Since the carbon films can be produced under low temperatures and thus can be produced on any kind of substrates. It is also possible to produce carbon films having a very high light transmission coefficient. Since the carbon films are produced through a sputtering process, the carbon films are secured on the substrates under strong adhesion forces. The carbon films have a spin density lower than is obtained through prior art methods. This permits the carbon films to have a widen optical band gap so as to increase its specific resistance.
  • a heater may be provided for heating the substrates 62 and 64 in order to produce carbon films through a high-temperature process.
  • a cooling pipe may be provided for passing a coolant such as water, liquid nitrogen or the like to cool the substrates 62 and 64 in order to produce carbon films through a low-temperature process.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Physical Vapour Deposition (AREA)
  • Chemical Vapour Deposition (AREA)
EP87101271A 1986-01-31 1987-01-30 Verfahren zur Herstellung eines Kohlenstoffilmes Expired - Lifetime EP0231894B1 (de)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP61019570A JPS62180057A (ja) 1986-01-31 1986-01-31 炭素薄膜の製造方法
JP19568/86 1986-01-31
JP61019569A JPH0742570B2 (ja) 1986-01-31 1986-01-31 炭素薄膜の製造方法
JP61019568A JPS62180055A (ja) 1986-01-31 1986-01-31 炭素薄膜の製造方法
JP19570/86 1986-01-31
JP19566/86 1986-01-31
JP19567/86 1986-01-31
JP19569/86 1986-01-31
JP61019567A JPS62180054A (ja) 1986-01-31 1986-01-31 炭素薄膜の製造方法
JP1956686A JPH079059B2 (ja) 1986-01-31 1986-01-31 炭素薄膜の製造方法

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EP0231894A1 true EP0231894A1 (de) 1987-08-12
EP0231894B1 EP0231894B1 (de) 1991-12-11

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US (1) US5073241A (de)
EP (1) EP0231894B1 (de)
KR (1) KR940002750B1 (de)
CA (1) CA1309057C (de)
DE (1) DE3775076D1 (de)
DK (1) DK168337B1 (de)

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DE3821614A1 (de) * 1988-06-27 1989-12-28 Licentia Gmbh Deckschicht aus amorphem kohlenstoff auf einem substrat, verfahren zur herstellung der deckschicht und verwendung der deckschicht
EP0395198A2 (de) * 1989-04-28 1990-10-31 Digital Equipment Corporation Zusammensetzungen von wasserstoffhaltigem Kohlenstoff
US5045165A (en) * 1990-02-01 1991-09-03 Komag, Inc. Method for sputtering a hydrogen-doped carbon protective film on a magnetic disk
US5232570A (en) * 1991-06-28 1993-08-03 Digital Equipment Corporation Nitrogen-containing materials for wear protection and friction reduction
US5750422A (en) * 1992-10-02 1998-05-12 Hewlett-Packard Company Method for making integrated circuit packaging with reinforced leads
GB2325473A (en) * 1997-05-23 1998-11-25 Univ Houston A method of depositing a carbon film on a membrane
WO2013190141A1 (de) * 2012-06-22 2013-12-27 Von Ardenne Anlagentechnik Gmbh Verfahren und vorrichtung zur vorbehandlung eines beschichteten oder unbeschichteten substrats
DE102005057833B4 (de) * 2005-01-12 2016-11-17 Frato Gmbh Aromabehältnis oder Aromafolie aus Aluminium

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US5275850A (en) * 1988-04-20 1994-01-04 Hitachi, Ltd. Process for producing a magnetic disk having a metal containing hard carbon coating by plasma chemical vapor deposition under a negative self bias
JPH06279185A (ja) * 1993-03-25 1994-10-04 Canon Inc ダイヤモンド結晶およびダイヤモンド結晶膜の形成方法
TW366367B (en) * 1995-01-26 1999-08-11 Ibm Sputter deposition of hydrogenated amorphous carbon film
RU2095464C1 (ru) * 1996-01-12 1997-11-10 Акционерное общество закрытого типа "Тетра" Биокарбон, способ его получения и устройство для его осуществления
US5827408A (en) * 1996-07-26 1998-10-27 Applied Materials, Inc Method and apparatus for improving the conformality of sputter deposited films
US6835279B2 (en) * 1997-07-30 2004-12-28 Hitachi Kokusai Electric Inc. Plasma generation apparatus
US6440220B1 (en) * 1998-10-23 2002-08-27 Goodrich Corporation Method and apparatus for inhibiting infiltration of a reactive gas into porous refractory insulation
US6352430B1 (en) 1998-10-23 2002-03-05 Goodrich Corporation Method and apparatus for cooling a CVI/CVD furnace
US6162298A (en) * 1998-10-28 2000-12-19 The B. F. Goodrich Company Sealed reactant gas inlet for a CVI/CVD furnace
US6964731B1 (en) 1998-12-21 2005-11-15 Cardinal Cg Company Soil-resistant coating for glass surfaces
US6974629B1 (en) 1999-08-06 2005-12-13 Cardinal Cg Company Low-emissivity, soil-resistant coating for glass surfaces
US6660365B1 (en) 1998-12-21 2003-12-09 Cardinal Cg Company Soil-resistant coating for glass surfaces
EP1063318B1 (de) 1999-06-04 2004-08-25 Goodrich Corporation Suzeptordeckel sowohl für Gasphaseninfiltration bzw. -Beschichtung als auch Wärmebehandlung
DE60005888T2 (de) 1999-06-04 2004-07-29 Goodrich Corp. Verfahren und Vorrichtung zur Druckmessung in einer CVD/CVI-Kammer
US6639196B1 (en) 1999-06-04 2003-10-28 Goodrich Corporation Method and apparatus for cooling a CVI/CVD furnace
BR0105474A (pt) * 2001-09-26 2003-09-23 Fundacao De Amparo A Pesquisa Processo de deposição de filme de carbono amorfo hidrogenado, filme de carbono amorfo hidrogenado e artigo revestido com filme de carbono amorfo hidrogenado
KR20030064942A (ko) * 2002-01-29 2003-08-06 오승준 스크래치 방지막을 가지는 조리 기구 및 그 제조방법
US7294404B2 (en) 2003-12-22 2007-11-13 Cardinal Cg Company Graded photocatalytic coatings
US7713632B2 (en) 2004-07-12 2010-05-11 Cardinal Cg Company Low-maintenance coatings
US8092660B2 (en) 2004-12-03 2012-01-10 Cardinal Cg Company Methods and equipment for depositing hydrophilic coatings, and deposition technologies for thin films
US7923114B2 (en) 2004-12-03 2011-04-12 Cardinal Cg Company Hydrophilic coatings, methods for depositing hydrophilic coatings, and improved deposition technology for thin films
EP1911859A4 (de) * 2005-07-04 2009-08-05 Nat Inst Of Advanced Ind Scien Kohlenstofffilm
WO2007124291A2 (en) * 2006-04-19 2007-11-01 Cardinal Cg Company Opposed functional coatings having comparable single surface reflectances
US20080011599A1 (en) 2006-07-12 2008-01-17 Brabender Dennis M Sputtering apparatus including novel target mounting and/or control
KR101563197B1 (ko) 2007-09-14 2015-10-26 카디날 씨지 컴퍼니 관리 용이한 코팅 및 이의 제조방법
WO2009118034A1 (de) * 2008-03-27 2009-10-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur herstellung eines mehrkomponentigen, polymer- und metallhaltigen schichtsystems, vorrichtung und beschichteter gegenstand
CN102102171A (zh) * 2011-01-28 2011-06-22 南通扬子碳素股份有限公司 表面沉积非晶碳薄膜降低石墨电极消耗的方法
US9763287B2 (en) * 2011-11-30 2017-09-12 Michael R. Knox Single mode microwave device for producing exfoliated graphite
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Cited By (14)

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US5122249A (en) * 1988-06-27 1992-06-16 Licentia Patent-Verwaltungs-Gmbh Method of producing a cover layer of amorphous carbon on a substrate
DE3821614A1 (de) * 1988-06-27 1989-12-28 Licentia Gmbh Deckschicht aus amorphem kohlenstoff auf einem substrat, verfahren zur herstellung der deckschicht und verwendung der deckschicht
US5750210A (en) * 1989-04-28 1998-05-12 Case Western Reserve University Hydrogenated carbon composition
EP0395198A3 (de) * 1989-04-28 1990-12-19 Digital Equipment Corporation Zusammensetzungen von wasserstoffhaltigem Kohlenstoff
US5266409A (en) * 1989-04-28 1993-11-30 Digital Equipment Corporation Hydrogenated carbon compositions
EP0395198A2 (de) * 1989-04-28 1990-10-31 Digital Equipment Corporation Zusammensetzungen von wasserstoffhaltigem Kohlenstoff
US5045165A (en) * 1990-02-01 1991-09-03 Komag, Inc. Method for sputtering a hydrogen-doped carbon protective film on a magnetic disk
US5397644A (en) * 1990-02-01 1995-03-14 Komag, Incorporated Magnetic disk having a sputtered hydrogen-doped carbon protective film
US5232570A (en) * 1991-06-28 1993-08-03 Digital Equipment Corporation Nitrogen-containing materials for wear protection and friction reduction
US5750422A (en) * 1992-10-02 1998-05-12 Hewlett-Packard Company Method for making integrated circuit packaging with reinforced leads
GB2325473A (en) * 1997-05-23 1998-11-25 Univ Houston A method of depositing a carbon film on a membrane
GB2325473B (en) * 1997-05-23 2001-11-28 Univ Houston Method for depositing a carbon film on a membrane
DE102005057833B4 (de) * 2005-01-12 2016-11-17 Frato Gmbh Aromabehältnis oder Aromafolie aus Aluminium
WO2013190141A1 (de) * 2012-06-22 2013-12-27 Von Ardenne Anlagentechnik Gmbh Verfahren und vorrichtung zur vorbehandlung eines beschichteten oder unbeschichteten substrats

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KR870007298A (ko) 1987-08-18
DK53087D0 (da) 1987-02-02
DK53087A (da) 1987-08-01
US5073241A (en) 1991-12-17
KR940002750B1 (ko) 1994-04-02
DK168337B1 (da) 1994-03-14
DE3775076D1 (de) 1992-01-23
EP0231894B1 (de) 1991-12-11
CA1309057C (en) 1992-10-20

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